Selective production of pentaethylenehexamine and hydroxyethyltriethylenetetramine

ABSTRACT

This invention relates to a process for making amines having a high yield weight percent of pentaethylenehexamine (PEHA) and hydroxyethyltriethylenetetramine (HETETA) by condensing an amino compound in the presence of a condensation catalyst selected from a Group IVB metal oxide, a Group VIB metal-containing substance and a promoted condensation catalyst. This invention also relates to an alkyleneamines producers composition rich in PEHA and HETETA.

RELATED APPLICATIONS

The following are related, commonly assigned applications, filed on aneven date herewith; U.S. patent application Ser. No. 501,917; U.S.patent application Ser. No. 501,919; U.S. patent application Ser. No.501,906; U.S. patent application Ser. No. 501,907; U.S. patentapplication Ser. No. 501,903; U.S. patent application Ser. No. 501,998;and U.S. patent application Ser. No. 501,920; all incorporated herein byreference.

The following are related, commonly assigned applications: U.S. patentapplication Ser. No. 07/136,615, filed Dec. 22, 1987 now abandoned; U.S.patent application Ser. No. 07/390,829, filed Aug. 8, 1989; U.S. patentapplication Ser. No. 07/390,706, filed Aug. 8, 1989; U.S. patentapplication Ser. No. 07/390,709, filed Aug. 8, 1989 (now U.S. Pat. No.4,983,736); U.S. patent application Ser. No. 07/390,828, filed Aug. 8,1989 (now U.S. Pat. No. 5,101,074); U.S. patent application Ser. No.07/390,708, filed Aug. 8, 1989; and U.S. patent application Ser. No.07/390,714, filed Aug. 8, 1989 (now abandoned in favor of continuationSer. No. 07/742,731, filed Aug. 16, 1991, which in turn has beenabandoned in favor of continuation Ser. No. 934,901, filed Aug. 26,1992); all incorporated herein by reference.

BRIEF SUMMARY OF THE INVENTION Technical Field

This invention relates to a process for making amines having a highyield weight percent of pentaethylenehexamine (PEHA) andhydroxyethyltriethylenetetramine (HETETA) by condensing an aminocompound in the presence of a condensation catalyst selected from aGroup IVB metal oxide, a Group VIB metal-containing substance and apromoted condensation catalyst.

This invention also relates to an alkyleneamines producers compositionrich in PEHA and HETETA.

BACKGROUND OF THE INVENTION

There is a substantial body of literature directed to the use of variousacid catalysts to effect intramolecular and intermolecular condensationof amino compounds. U.S. Pat. No. 2,073,671 and U.S. Pat. No. 2,467,205constitute early prior work on the use of acid condensation catalysts tocondense amino compounds. U.S. Pat. No. 2,073,671 discusses, in ageneral fashion, the catalytic intermolecular condensation of alcoholsand amines or ammonia using the same phosphate catalysts later favoredby U.S. Pat. No. 2,467,205 for the intramolecular condensation ofamines. The two patents are not in harmony over the use of othermaterials as catalysts. To illustrate this point, U.S. Pat. No.2,073,671 states:

"Alumina, thoria, blue oxide of tungsten, titania, chromic oxide, blueoxide of molybdenum and zirconia have been mentioned in the literaturefor use as catalysts in carrying out these reactions but theireffectiveness is so low that no practical application has been made oftheir use."

whereas U.S. Pat. No. 2,467,205 in describing the self-condensation ofethylenediamine (EDA) under vapor phase conditions, to initially produceethyleneamines, but after recycle, eventually generates piperazine (PIP)through multistep condensation reactions, followed by deamination,recommends "dehydration catalysts" which are thereafter characterized as

"silica gel, titania gel, alumina, thoria, boron phosphate, aluminumphosphate, and the like."

U.S. Pat. No 2,073,671 describes the condensation catalyst in thefollowing terms:

". . . a heated catalyst or contact mass containing phosphorus andespecially one or more of the oxygen acids of phosphorus, theiranhydrides, their polymers, and their salts; for example,orthophosphoric acid, metaphosphoric acid, Pyrophosphoric acid,phosphorous pentoxide, dimetaphosphoric acid, trimetaphosphoric acid,primary ammonium phosphate, secondary ammonium phosphate, normalammonium phosphate, ammonium metaphosphate, secondary ammoniumpyrophosphate, normal ammonium pyrophosphate, aluminum phosphate,aluminum acid phosphate and mixtures of two or more of such materials."

whereas U.S. Pat. No. 2,467,205 describes one of the preferred catalystsas "basic aluminum phosphate".

U.S. Pat. No. 2,454,404 describes the "catalytic deamination of alkylenepolyamines" by reacting DETA vapor over solid catalysts such asactivated alumina, bauxite, certain aluminum silicates such as kaolinand oxides of thorium, titanium and zirconium.

U.S. Pat. Nos. 2,073,671 and 2,467,205 demonstrate a common experiencein using aluminum phosphate as a condensation catalyst to producealiphatic amines, and U.S. Pat. Nos. 2,454,404 and 2,467,205 contemplatethe other solid catalysts for deamination of amines to make heterocyclicnoncyclic amines. In general, the reaction conditions under whichdeamination to effect cyclization occurs are more severe than thoseemployed for condensation to generate noncyclic molecules, all otherfactors being comparable.

U.S. Pat. Nos. 4,540,822, 4,584,406 and 4,588,842 depict the use ofGroup IVB metal oxides as supports for phosphorus catalysts used toeffect the condensation of amino compounds with alkanolamines.

U.S. Pat. No. 4,683,335 describes the use of tungstophosphoric acid,molybdophosphoric acid or mixtures deposited on titania as catalysts forthe condensation of amines and alkanolamines to makepolyalkylenepolyamines.

U.S. Pat. Nos. 4,314,083, 4,316,840, 4,362,886 and 4,394,524 disclosethe use of certain metal sulfates as useful catalysts for thecondensation of alkanolamine and an amino compound. No distinction ismade between the sulfur compounds in respect to catalytic efficacy.Sulfuric acid is as good as any metal sulfate, and all metal sulfatesare treated as equivalents. At column 8 of U.S. Pat. No. 4,314,083, itis noted that boron sulfate "gave extremely high selectivity at a lowlevel" of EDA. However, selectivity in general was shown to increasewith an increase of EDA relative to monoethanolamine (MEA) in the feed.The only specific metal sulfates disclosed in the patents are antimonysulfate, beryllium sulfate, iron sulfate and aluminum sulfate.

In the typical case of the manufacture of alkyleneamines, mixtures withother alkyleneamines (including a variety of polyalkylenepolyamines andcyclic alkylenepolyamines) are formed. The same holds true when theobject of the process is to produce polyalkylenepolyamines whetheracyclic or cyclic, in that a variety of amino compounds are also formed.Each of these cyclic and acyclic alkyleneamines can be isolated from themixture.

The acid catalyzed condensation reaction involving the reaction of analkanolamine with an amino compound in the presence of an acidiccatalyst is believed to proceed through the mechanism of esterifyingfree surface hydroxyl groups on the acid catalyst with the alkanolamineand/or by protonating the alkanolamine in the presence of the acidcatalyst, followed by loss of water and amine condensation of the esteror the hydrated species, as the case may be, to form the alkyleneamine.Illustrative prior art directed primarily to the cyclicpolyalkylenepolyamines (heterocyclic polyamines), but not necessarilylimited to the aforementioned acid condensation reaction, are: U.S. Pat.Nos. 2,937,176, 2,977,363, 2,977,364, 2,985,658, 3,056,788, 3,231,573,3,167,555, 3,242,183, 3,297,701, 3,172,891, 3,369,019, 3,342,820,3,956,329, 4,017,494, 4,092,316, 4,182,864, 4,405,784 and 4,514,567;European Patent Applications 0 069 322, 0 111 928 and 0 158 319; EastGerman Pat. No. 206,896; Japanese Patent Publication No. 51-141895; andFrench Patent No. 1,381,243. The evolution of the art to the use of theacid catalyzed condensation reaction to generate acyclic alkyleneamines,particularly acyclic polyalkylenepolyamines, as the predominant productsstemmed from the initial disclosure in U.S. Pat. No. 4,036,881, thoughearlier patent literature fairly well characterized such an effectwithout labeling it so, see U.S. Pat. No. 2,467,205, supra. The acidcatalysts are phosphorus compounds and the reaction is carried out inthe liquid phase. The trend in this catalyst direction was early set asdemonstrated by U.S. Pat. Nos. 2,073,671 and 2,467,205, supra. Amodification of this route includes the addition of ammonia to thereaction, see, for example, U.S. Pat. No. 4,394,524 and U.S. Pat. No.4,463,193 for the purpose of converting alkanolamine such as MEA in situto alkylene amine such as EDA by reaction with ammonia, and the EDA isin situ reacted with MEA according to the process of U.S. Pat. No.4,036,881 to form alkyleneamines.

A summary of the prior art employing acid catalysts for makingalkyleneamines is set forth in Table I below.

                                      TABLE I                                     __________________________________________________________________________    CITATION    CATALYST TYPE    REACTANTS                                        __________________________________________________________________________    U.S. Pat. No. 2,467,205                                                                   Silica gel, titania gel, alumina                                                               Vapor phase condensation of                                  thoria, aluminum phosphate.                                                                    EDA over a fixed bed of the                                  Preferred catalyst is basic                                                                    catalyst, multipass process                                  aluminum phosphate.                                                                            shifts from polyethylene-                                                     polyamines with the first few                                                 cycles.                                          U.S. Pat. No. 4,036,881                                                                   Phosphorus containing substances                                                               Alkanolamine and alkylene-                                   selected from the group consisting                                                             amine in liquid phase                                        of acidic metal phosphates,                                                                    reaction.                                                    phosphoric acid compounds and                                                 their anhydrides, phosphorus acid                                             compounds and their anhydrides,                                               alkyl or aryl phosphate esters,                                               alkyl or aryl phosphite esters,                                               alkyl or aryl substituted                                                     phosphorous and phosphoric acids                                              wherein said alkyl groups have                                                from 1 to about 8 carbon atoms and                                            said aryl groups have from 6 to                                               about 20 carbon atoms, alkali                                                 metal monosalts of phosphoric                                                 acid, the thioanalogs of the fore-                                            going, and mixtures of the above.                                 U.S. Pat. No. 4,044,053                                                                   Phosphorus containing substances                                                               Alkanepolyols and alkylene-                                  selected from the group consisting                                                             amine in liquid phase                                        of acidic metal phosphates,                                                                    reaction.                                                    phosphoric acid compounds and                                                 their anhydrides, phosphorus                                                  acid compounds and their                                                      anhydrides, alkyl or aryl                                                     phosphate esters, alkyl or aryl                                               phosphite esters, alkyl or aryl                                               substituted phosphorous acids and                                             phosphoric acids wherein said                                                 alkyl groups have from 1 to about                                             8 carbon atoms and said aryl                                                  groups have from 6 to about 20                                                carbon atoms, alkali metal mono-                                              salts of phosphoric acid and                                                  mixtures of the above.                                            U.S. Pat. No. 4,314,083                                                                   Salt of a nitrogen or sulfur con-                                                              Alkanolamine and an                                          taining substance or the corres-                                                               alkyleneamine in liquid                                      ponding acid.    phase reaction.                                  U.S. Pat. No. 4,316,840                                                                   Metal nitrates and sulfates                                                                    Reforming linear polyamines.                                 including zirconium sulfate.                                      U.S. Pat. No. 4,316,841                                                                   Phosphate, perferably boron                                                                    Reforming linear polyamines.                                 phosphate.                                                        U.S. Pat. No. 4,324,917                                                                   Phosphorus-containing cation                                                                   Alkanolamine and an alkylene-                                exchange resin.  amine in liquid phase                                                         reaction.                                        U.S. Pat. No. 4,362,886                                                                   Arsenic, antimony or bismuth                                                                   Alkanolamie and an alkylene-                                 containing compounds. Antimony                                                                 amine in liquid phase                                        sulfate specifically disclosed.                                                                reaction.                                        U.S. Pat. No. 4,399,308                                                                   Lewis acid halide.                                                                             Alkanolamine and an alkylene-                                                 amine in liquid phase                                                         reaction.                                        U.S. Pat. No. 4,394,524                                                                   Phosphorus-containing substance                                                                Ammonia, alkanolamine and an                                 or salt of a sulfur-containing                                                                 alkyleneamine in liquid phase                                substance, or the corresponding                                                                reaction.                                                    acid.                                                             U.S. Pat. No. 4,448,997                                                                   Reacts alumina with phosphoric                                                                 EDA with MEA.                                                acid, adds ammonium hydroxide.                                    U.S. Pat. No. 4,463,193                                                                   Group IIIB metal acid phosphate.                                                               Ammonia, alkanolamine and                                                     an alkyleneamine.                                U.S. Pat. No. 4,503,253                                                                   Supported phosphoric acid.                                                                     Ammonia, alkanolamine and                                                     an alkyleneamine.                                U.S. Pat. No. 4,521,600                                                                   Select hydrogen phosphates and                                                                 Alkanolamine and an alkylene-                                pyrophosphates.  amine.                                           U.S. Pat. No. 4,524,143                                                                   Phosphorus impregnated onto                                                                    Alkanolamine and an alkylene-                                zirconium silicate support.                                                                    amine.                                           U.S. Pat. No. 4,540,822                                                                   Phosphorus compound deposited                                                                  Alkanolamine and an alkylene-                                on a Group IVB metal oxide                                                                     amine, regenerates the                                       support.         catalyst with O.sub.2 -containing                                             gas.                                             U.S. Pat. No. 4,547,591                                                                   Silica-alumina alone or in                                                                     An ethyleneamine and an                                      combination with an acidic                                                                     alkanolamine; ethyleneamines;                                phosphorus cocatalyst.                                                                         or ammonia and an alkanol-                                                    amine.                                           U.S. Pat. No. 4,550,209                                                                   An intercalatively catalytically                                                               EDA and MEA.                                                 active tetravalent zirconium                                                  polymeric reaction product of an                                              organo phosphonic acid or an                                                  ester thereof with a compound of                                              tetravalent zirconium reactive                                                therewith.                                                        U.S. Pat. No. 4,552,961                                                                   Phosphorus amide compound.                                                                     Alkyleneamine and alkanolamine                                                and/or alkylene glycol.                          U.S. Pat. No. 4,555,582                                                                   Phosphorus chemically bonded to                                                                MEA and EDA.                                                 a zirconium silicate support.                                     U.S. Pat. No. 4,560,798                                                                   Rare earth metal or strontium                                                                  MEA.                                                         acid phosphate.                                                   U.S. Pat. No. 4,578,517                                                                   Group IIIB metal acid phosphate.                                                               Ammonia or p-/s-amine                                                         and alkanolamine.                                U.S. Pat. No. 4,578,518                                                                   Thermally activated, calcined,                                                                 MEA and EDA.                                                 pelleted titania containing                                                   titanium triphosphate. ". . . the                                             titania that was used was . . .                                               anatase." (Col. 9, lines 18-19).                                  U.S. Pat. No. 4,578,519                                                                   Thermally activated, calcined,                                                                 MEA and EDA with optional                                    pelleted titania with chemically                                                               recycle of DETA.                                             bonded phosphorus derived from                                                polyphosphoric acid.                                              U.S. Pat. No. 4,584,405                                                                   Activated carbon, optionally                                                                   MEA and EDA.                                                 treated to incorporate phosphorus.                                            Activated carbon may be washed                                                with strong mineral acid to                                                   remove impurities followed by                                                 water wash. Optional treatment                                                follows.                                                          U.S. Pat. No. 4,584,406                                                                   Pelleted Group IVB metal oxide                                                                 MEA and EDA.                                                 with chemically bonded phosphorus                                             derived from phosphoryl chloride                                              or bromide.                                                       U.S. Pat. No. 4,588,842                                                                   Thermally activated pelleted                                                                   MEA and EDA.                                                 Group IVB metal oxide with                                                    chemically bonded phosphorus.                                     U.S. Pat. No. 4,605,770                                                                   Group IIA or IIIB metal acid                                                                   Alkanolamine and an                                          phosphate.       alkyleneamine "in liquid                                                      phase".                                          U.S. Pat. No. 4,609,761                                                                   Thermally activated pelleted                                                                   MEA and EDA.                                                 titania with chemically bonded                                                phosphorus.                                                       U.S. Pat. No. 4,612,397                                                                   Thermally activated pelleted                                                                   MEA and EDA.                                                 titania with chemically bonded                                                phosphorus.                                                       U.S. Pat. No. 4,617,418                                                                   Acid catalysts, mentions "beryl-                                                               Ammonia, alkanolamine and                                    lium sulfate".   an alkyleneamine "under                                                       vapor phase conditions".                         Japanese Patent                                                                           Variety of phosphorus and metal                                                                Ammonia, alkanolamine and                        Application phosphates including Group IVB                                                                 ethyleneamine, with ammonia/                     #1983-185,871,                                                                            phosphates.      alkanolamine molar ratio                         Publication                  greater than 11.                                 #1985-78,945                                                                  U.S. Pat. No. 4,683,335                                                                   Tungstophosphoric acid, molybdo-                                                               Claims reaction of MEA and                                   phosphoric acid or mixtures                                                                    EDA, but discloses self-                                     deposited on titania. Examples                                                                 condensation reaction of                                     2-7 characterize titania surface                                                               EDA and DETA.                                                areas of 51, 60 and 120 m.sup.2 /gm.                              Japanese Patent                                                                           Group IVB metal oxide with                                                                     Ammonia and MEA.                                 Application bonded phosphorus.                                                #1985-078,391,                                                                Publication                                                                   #1986-236,752                                                                 Japanese Patent                                                                           Group IVB metal oxide with                                                                     Ammonia and MEA.                                 Application bonded phosphorus.                                                #1985-078,392,                                                                Publication                                                                   #1986-236,753                                                                 U.S. Pat. No. 4,698,427                                                                   Titania having phosphorus                                                                      Diethanolamine and/or                                        thermally chemically bonded                                                                    hydroxyethyldiethylene-                                      to the surface thereof in the                                                                  triamine in EDA.                                             form of phosphate bonds.                                          U.S. Pat. No. 4,806,517                                                                   Pelleted Group IVB metal oxide                                                                 MEA and EDA.                                                 with phosphorus thermally                                                     chemically bonded to the                                                      surface thereof.                                                  European Patent                                                                           Titania and zirconia chemically                                                                MEA and EDA.                                     Application bonded to phosphorus.                                             331,396                                                                       __________________________________________________________________________

A summary of additional prior art for making alkyleneamines is set forthin Table II below.

                                      TABLE II                                    __________________________________________________________________________    CITATION CATALYST TYPE    REACTANTS                                           __________________________________________________________________________    Japanese Patent                                                                        Niobium-containing                                                                             Ammonia, alkyleneamine                              Application                                                                            substance.       and alkylene glycol.                                #1987-312,182,                                                                Publication                                                                   #1989-153,659                                                                 Japanese Patent                                                                        Niobium-containing                                                                             Ammonia, alkyleneamine                              Application                                                                            substance added  and alkanolamine.                                   #1987-325,274,                                                                         to water-containing liquid.                                          Publication                                                                   #1989-168-647                                                                 Japanese Patent                                                                        Niobium oxide    Ammonia, alkyleneamine                              Application                                                                            obtained from    and alkanolamine                                    #1987-321,348,                                                                         niobium alkoxide.                                                    Publication                                                                   #1989-163,159                                                                 Japanese Patent                                                                        Niobium pentoxide.                                                                             Ammonia, alkyleneamine                              Application               and dialkanolamine.                                 #1989-314,132,                                                                Publication                                                                   #1989-157,936                                                                 Japanese Patent                                                                        Niobium-containing                                                                             Ammonia, alkyleneamine                              Application                                                                            substance.       and alkanolamine.                                   #1987-290,652,                                                                Publication                                                                   #1989-132,550                                                                 Japanese Patent                                                                        Tantalum-containing                                                                            Ammonia, alkyleneamine                              Application                                                                            substance.       and alkanolamine.                                   #1987-142,284,                                                                Publication                                                                   #1988-307,846                                                                 European Patent                                                                        Mixed oxide      Ammonia, alkyleneamine                              Application                                                                            containing niobium                                                                             and alkanolamine.                                   315,189  oxide.                                                               European Patent                                                                        Niobium-containing                                                                             Ammonia, alkyleneamine                              Application                                                                            substance supported                                                                            and alkanolamine.                                   328,101  on a carrier.                                                        Japanese Patent                                                                        Titania and zirconia                                                                           MEA and EDA.                                        Application                                                                            chemically bonded with                                               #1989-048,699,                                                                         phosphorus in the form                                               Publication                                                                            of a hydroxy-containing                                              #1990-006,854                                                                          phosphate group.                                                     Japanese Patent                                                                        Niobium oxide and titania,                                                                     Ammonia, alkyleneamine                              Application                                                                            alumina, silica or zirconia.                                                                   and alkanolamine.                                   #1988-262,861,                                                                Publication                                                                   #1990-002,876                                                                 Japanese Patent                                                                        Niobium oxide treated with                                                                     Ammonia, alkyleneamine                              Application                                                                            an acid.         and alkanolamine.                                   #1988-290,106,                                                                Publication                                                                   #1990-000,735                                                                 Japanese Patent                                                                        Niobium-containing                                                                             Ammonia, alkyleneamine                              Application                                                                            substance on a carrier.                                                                        and alkanolamine.                                   #1988-027,489,                                                                Publication                                                                   #1990-000,736                                                                 Japanese Patent                                                                        Three constituent catalyst-                                                                    Alcohol or aldehyde and                             Application                                                                            copper; one or more elements                                                                   ammonia, a primary                                  #1988-261,366                                                                          selected from chromium,                                                                        amine or a secondary amine.                         Publication                                                                            manganese, iron and zinc;                                            #1990-000,232                                                                          and a platinum group element.                                        Japanese Patent                                                                        Four constituent catalyst-copper;                                                              Alcohol or aldehyde                                 Application                                                                            one or more elements selected                                                                  and ammonia, a primary                              #1988-261,368,                                                                         from chromium, manganese, iron,                                                                amine or a secondary amine.                         Publication                                                                            cobalt, nickel and zinc;                                             #1990-000,233                                                                          a platinum group element; and                                                 one or more elements selected                                                 from lithium, sodium, potassium,                                              rubidium, cesium, magnesium,                                                  calcium, strontium and barium.                                       Japanese Patent                                                                        Four constituent catalyst-copper;                                                              Alcohol or aldehyde and                             Application                                                                            one or more elements selected from                                                             ammonia, a primary amine                            #1988-261,369,                                                                         chromium, manganese, iron, cobalt,                                                             or a secondary amine.                               Publication                                                                            nickel and zinc; a platium group                                     #1990-000,234                                                                          element; and one or more elements                                             selected from aluminum, tungsten                                              and molybdenum.                                                      __________________________________________________________________________

A market demand for PEHA and HETETA has been progressively developing inrecent years. It would be desirable to satisfy this developing demandfrom a cost standpoint by modifying slightly the commercial processesdirected to the manufacture of polyalkylene polyamines from suitablestarting raw materials to the production of PEHA and HETETA as majorproducts.

It would be desirable to have continuously produced compositions,generated by the reaction of dihydroxyethylethylenediamine (DiHEED) andEDA or other suitable starting raw materials over a fixed bed of acondensation catalyst under commercial conditions, that are rich in PEHAand HETETA and that are not disproportionately high in cyclics.

The above features are provided by this invention.

SUMMARY OF THE INVENTION

This invention relates in general to a process of making amines having ahigh yield weight percent of PEHA and HETETA which comprises condensingan amino compound in the presence of a condensation catalyst selectedfrom a Group IVB metal oxide, a Group VIB metal-containing substance anda promoted condensation catalyst. The amino compound used hereinpreferably comprises an alkyleneamine and a dialkanoldiamine, inparticular, EDA and DiHEED. The condensation catalysts used hereincontain sufficient residual bound hydroxyl groups or other groupingswhich renders catalyst formation possible by loss of water or itschemical equivalent such as ammonium hydroxide.

More particularly, this invention relates to a process of making amineshaving a high yield weight percent of PEHA and HETETA by the (i)intramolecular condensation of an amino compound to an amine having alower molecular weight or (ii) the intermolecular condensation of anamino compound with one or more of another amino compound or a compoundcontaining an alcoholic hydroxyl group using a particularly definedcondensation catalyst. The process of this invention primarily involvesintermolecular condensation reactions. A preferred process involves themanufacture of PEHA and HETETA by an intermolecular condensationreaction utilizing EDA and DiHEED as reactants and a Group VIBmetal-containing substance or a Group IVB metal oxide as thecondensation catalyst.

The invention further relates to a continuously generated alkyleneaminesproducers composition comprising, based on 100 percent of the weight ofthe composition and exclusive of any water and/or ammonia and/or feedpresent,

a) greater than about 8.0 weight percent of PEHA,

b) greater than about 10.0 weight percent of HETETA,

c) less than about 30.0 weight percent of PEEDA+HEP,

d) less than about 35.0 weight percent of others,

e) a HETETA to PEHA weight ratio of less than about 10.0, and

f) a PEHA+HETETA to PEEDA weight ratio of greater than about 2.0.

As used herein, the term "amino compound" embraces ammonia and anycompound containing nitrogen to which is bonded an active hydrogen.Also, as used herein, the term "oxide" embraces oxides, hydroxidesand/or mixtures thereof. Further, as used herein, the term "others"embraces polyalkylene polyamines, byproducts and the like.

For purposes of this invention, the chemical elements are identified inaccordance with the Periodic Table of the Elements, CAS version,Handbook of Chemistry and Physics, 67th Ed., 1986-87, inside cover.Also, for purposes of this invention, Group IIIB metal oxides embracesthe lanthanides and actinides. Further, for purposes of this invention,DiHEED embraces N,N'-bis(2-hydroxyethyl)ethylenediamine,N,N-bis(2-hydroxyethyl)ethylenediamine and mixtures thereof.

DETAILED DESCRIPTION

PEHA and HETETA are very useful commercial products for a variety ofapplications including fuel oil additives, corrosion inhibitors, fabricsofteners, epoxy curing agents and others. There is a developing needfor the ability to commercially generate larger production quantities ofPEHA and HETETA and that is the direction of this invention. The processof this invention provides for the reaction of DiHEED and EDA or othersuitable starting raw materials to produce in a continuous manner areaction product mixture, termed herein an "alkyleneamines producerscomposition", in which PEHA and HETETA are principal products of thereaction.

The process of this invention is distinctive insofar as it achieves thegeneration of high concentrations of PEHA and HETETA in a manner whichcan be suitably employed in a commercial process, particularly acontinuous process, for the manufacture of alkyleneamines. Inparticular, the process of this invention allows the production of PEHAand HETETA in relatively high yields without generating large amounts ofcyclic alkyleneamine products.

As indicated above, this invention relates to a process of making amineshaving a high yield weight percent of PEHA and HETETA which comprisescondensing an amino compound in the presence of a catalyticallyeffective amount of a condensation catalyst selected from a Group IVBmetal oxide, a Group VIB metal-containing substance and a promotedcondensation catalyst. The amino compound preferably comprises analkyleneamine and a dialkanoldiamine, in particular, EDA and DiHEED.

A high yield weight percent of linear PEHA (L-PEHA) and HETETA can beobtained from the reaction of DiHEED and EDA when DiHEED is primarilycomprised of N,N'-bis(2-hydroxyethyl)ethylenediamine. A high yieldweight percent of branched PEHA can be obtained when DiHEED is primarilycomprised of N,N-bis(2-hydroxyethyl)ethylenediamine. Product selectivityis therefore dependent on the particular composition of DiHEED used inthe process of this invention.

As also indicated above, this invention relates to a continuouslygenerated alkyleneamines producers composition comprising, based on 100percent of the weight of the composition and exclusive of any waterand/or ammonia and/or feed present,

a) greater than about 8.0 weight percent of PEHA,

b) greater than about 10.0 weight percent of HETETA,

c) less than about 30.0 weight percent of PEEDA+HEP,

d) less than about 35.0 weight percent of others,

e) a HETETA to PEHA weight ratio of less than about 10.0, and

f) a PEHA+HETETA to PEEDA weight ratio of greater than about 2.0.

The alkyleneamines producers composition of this invention can besubjected to conventional separations techniques for recovering theindividual components of the composition. Such techniques are well knownin the art and include, for example, distillation.

This invention contemplates the catalyzed condensation by (i)intramolecular condensation of an amino compound to an amine having alower molecular weight, and (ii) intermolecular condensation of an aminocompound with one or more of another amino compound or a compoundcontaining an alcohol hydroxyl group to an amine having a lower, same orhigher molecular weight than the reactants, in the presence of aparticularly defined condensation catalyst. The process of thisinvention primarily involves intermolecular condensation reactions.

A wide variety of condensation catalysts can be used in this invention.Illustrative of suitable condensation catalysts for use in thisinvention include, for example, Group IVB metal oxides, Group VIBmetal-containing substances and promoted condensation catalysts.

The Group IVB metal oxide condensation catalysts are preferred catalystsfor use in this invention. Suitable Group IVB metal oxide condensationcatalysts are disclosed in U.S. patent application Ser. No. 07/390,829,filed Aug. 8, 1989 and incorporated herein by reference. Illustrative ofGroup IVB metal oxide condensation catalysts include, for example,titanium oxide and zirconium oxide, preferably titanium dioxide andzirconium dioxide including mixtures thereof.

The Group VIB metal-containing condensation catalysts are also preferredcatalysts for use in this invention. Suitable Group VIB metal-containingcondensation catalysts are disclosed in the above-cited related U.S.patent application Ser. No. 07/390,708, filed Aug. 8, 1989 andincorporated herein by reference. Illustrative of Group VIBmetal-containing condensation catalysts include, for example, one ormore oxides of tungsten, chromium, molybdenum or mixtures thereof.

A variety of promoted condensation catalysts are also desirable for usein this invention. Suitable promoted condensation catalysts aredisclosed in U.S. patent application Ser. No. 07/390,714, filed Aug. 8,1989 and incorporated herein by reference. The condensation catalystsare promoted by a condensation catalyst promoter as describedhereinafter. Illustrative of such condensation catalysts include, forexample, one or more Group IVB metal oxides and Group VIBmetal-containing substances.

The condensation catalyst promoter for use in this invention should becapable of promoting the condensation catalyst. The promoting effect canrelate to catalytic activity, product selectivity and/or catalyststability (mechanical or dimensional strength of the catalyst).Illustrative of condensation catalyst promoters for use in thisinvention can include, for example, one or more metal oxides, one ormore metallic phosphates which may or may not have a cyclic structure,one or more metallic polyphosphates having a condensed structure, one ormore Group VIB metal-containing substances and one or more conventionalmaterials such as mineral acids or compounds derived from mineral acids.Mixtures of condensation catalyst promoters may also be employed in thisinvention. For purposes of this invention, the condensation catalystpromoter should be different from the condensation catalyst; however,the condensaton catalyst promoter and the performance moderatordescribed hereinafter can be the same or different.

This invention also embraces the use of vicinal di(hetero)alkyleneorganometalates in the selective preparation of PEHA and HETETA.Suitable vicinal di(hetero)alkylene organometalates are disclosed inU.S. patent application Ser. No. 07/390,828, filed Aug. 8, 1989 andincorporated herein by reference (now U.S. Pat. No. 5,101,074).

The level of activity of the condensation catalysts of the invention isthat level which of itself makes the catalysts at least as active in thecondensation of amines as, for example, is phosphoric acid on anequivalent basis. Preferably, the condensation catalysts on a supportshould have a surface area greater than about 20 m² /gm to as high asabout 260 m² /gm or greater depending upon which metal oxide describedbelow that is employed. In the case of titanium oxides, the surface areashould be greater than about 140 m² /gm to as high as about 260 m² /gm,more preferably, greater than about 160 m² /gm to as high as about 260m² /gm, determined according to the single point N₂ method. In the caseof zirconia oxides, the surface area should be greater than about 70 m²/gm to as high as about 150 m² /gm, more preferably, greater than about90 m² /gm to as high as about 135 m² /gm, determined according to thesingle point N₂ method. It is appreciated that the performancemoderators described below which can be used in association with thecondensation catalyst and the condensation catalyst promoters describedabove can affect the surface area of the condensation catalyst. Whilesurface areas described above may be preferred, for purposes of thisinvention, the surface area of the condensation catalyst should besufficient to contribute to product selectivity, catalytic activityand/or mechanical or dimensional strength of the catalyst.

Though the condensation catalyst of the invention provides sufficientactivity to effect the condensation reaction, certain combinations ofreactants and/or product formation can be benefited by treating thecatalyst with a catalyst moderator, hereinafter termed a "performancemoderator". Performance moderators are widely used to promote theperformance of catalysts in areas of selectivity to certain products andthe repression of a catalyst's proclivity to generate a broad range ofreaction products. A range of suitable materials may impact thecondensation catalysts of this invention in the variety of reactionproducts. The performance moderator may be any material which impactsthe condensation catalyst's selection of reaction products or whichchanges the proportion of any one or more of the reaction products whichthe condensation catalyst generates at comparable processing conditions.In addition to contributing to product selectivity, the performancemoderator may be any material which contributes to catalytic activityand/or catalyst stability (mechanical or dimensional strength).

Illustrative performance moderators for use in this invention caninclude, for example, one or more metal oxides, one or more metallicphosphates which may or may not have a cyclic structure, one or moremetallic polyphosphates having a condensed structure, one or more GroupVIB metal-containing substances and one or more conventional materialssuch as mineral acids or compounds derived from mineral acids. Mixturesof performance moderators may also be employed in this invention. Forpurposes of this invention, the performance moderator should bedifferent from the condensation catalyst; however, the performancemoderator and the condensation catalyst promoter can be the same ordifferent.

Illustrative of metal oxides which may be utilized as performancemoderators in association with the condensation catalyst include, forexample, one or more of the following: Group IA metal oxides, Group IIAmetal oxides, Group IIIB metal oxides (including lanthanides andactinides), Group VB metal oxides, Group VIB metal oxides, Group VIIBmetal oxides, Group VIII metal oxides, Group IB metal oxides, Group IIBmetal oxides, Group IIIA metal oxides, Group IVA metal oxides, Group VAmetal oxides, Group VIA metal oxides and Group IVB metal oxides ormixtures thereof. Certain of these metal oxides may also be used ascondensation catalysts in accordance with this invention such as GroupIVA and IVB metal oxides. Preferred metal oxides are amphoteric orslightly acidic or slightly basic. Preferred metal oxides which may beutilized in association with the condensation catalyst include, forexample, one or more oxides of beryllium, scandium, yttrium, terbium,dysprosium, holmium, erbium, thulium, ytterbium, lutetium, titanium,zirconium, hafnium, vanadium, niobium, tantalum, tungsten, iron, cobalt,zinc, silver, aluminum, gallium, indium, silicon, germanium, tin, lead,arsenic, antimony and bismuth.

Group IVB metal oxides such as titanium dioxide and zirconium dioxideand Group IVA metal oxides such as silica and germania are preferred foruse in this invention. For mixed metal oxides in which at least one ofthe metals is titanium, suitable metals in association with titanium mayinclude, for example, one or more of the following: Group IIIB metalssuch as scandium, yttrium and lanthanum including the lanthanides, GroupVB metals such as niobium and tantalum, Group VIB metals such aschromium, molybdenum and tungsten, Group VIII metals such as iron,cobalt and nickel, Group IIB metals such as zinc and cadmium, Group IIIAmetals such as boron, aluminum, gallium and indium, Group IVA metalssuch as silicon, germanium, tin and lead, Group VA metals such asarsenic, antimony and bismuth, and Group IVB metals such as zirconiumand hafnium. For mixed metal oxides in which at least one of the metalsis zirconium, suitable metals in association with zirconium may include,for example, one or more of the following: Group IVA metals such assilicon, germanium, tin and lead, Group VB metals such as niobium andtantalum, and Group VIB metals such as chromium, molybdenum andtungsten. Certain of these metal oxides may also be effective ascondensation catalysts for use in this invention.

Illustrative of mixed metal oxides which may be used as performancemoderators in association with the condensation catalyst include, forexample, TiO₂ -SiO₂, TiO₂ -Al₂ O₃, TiO₂ -CdO, TiO₂ -Bi₂ O₃, TiO₂ -Sb₂O₅, TiO₂ -SnO₂, TiO₂ -ZrO₂, TgiO₂ -BeO, TiO₂ -MgO, TiO₂ -CaO, TiO₂ -SrO,TiO₂ -ZnO, TiO₂ -Ga₂ O₃, TiO₂ -Y₂ O₃, TiO₂ -La₂ O₃, TiO₂ -MoO₃, TiO₂-Mn₂ O₃, TiO₂ -Fe₂ O₃, TiO₂ -Co₃ O₄, TiO₂ -WO₃, TiO₂ -V₂ O₅, TiO₂ -Cr₂O₃, TiO₂ -ThO₂, TiO₂ -Na₂ O, TiO₂ -BaO, TiO₂ -CaO, TiO₂ -HfO₂, TiO₂ -Li₂O, TiO₂ -Nb₂ O₅, TiO₂ -Ta₂ O₅, TiO₂ -Gd₂ O₃, TiO₂ -Lu₂ O₃, TiO₂ -Yb₂ O₃,TiO₂ -CeO₂, TiO₂ -Sc₂ O₃ , TiO₂ -PbO, TiO₂ -NiO, TiO₂ -CuO, TiO₂ -CoO,TiO₂ -B₂ O₃, ZrO₂ -SiO₂, ZrO₂ -Al₂ O₃, ZrO₂ -SnO, ZrO₂ -PbO, ZrO₂ -Nb₂O₅, ZrO₂ -Ta₂ O₅, ZrO₂ -Cr₂ O₃, ZrO₂ -MoO₃, ZrO₂ -WO₃, ZrO₂ -TiO₂, ZrO₂-HfO₂, TiO₂ -SiO₂ -Al₂ O₃, TiO₂ -SiO₂ -ZnO, TiO₂ -SiO₂ -ZrO₂, TiO₂ -SiO₂-CuO, TiO₂ -SiO₂ -MgO, TiO₂ -SiO₂ -Fe₂ O₃, TiO₂ -SiO₂ -B₂ O₃, TiO₂ -SiO₂-WO₃, TiO₂ -SiO₂ -Na₂ O, TiO₂ -SiO₂ -MgO, TiO₂ -SiO₂ -La₂ O₃, TiO₂ -SiO₂-Nb₂ O₅, TiO₂ -SiO₂ -Mn₂ O₃, TiO₂ -SiO₂ -Co₃ O₄, TiO₂ -SiO₂ -NiO, TiO₂-SiO₂ -PbO, TiO₂ -SiO₂ -Bi₂ O.sub. 3, TiO₂ -Al₂ O₃ -ZnO, TiO₂ -Al₂ O₃-ZrO₂, TiO₂ -Al₂ O₃ -Fe₂ O₃, TiO₂ -Al₂ O₃ -WO₃, TiO₂ -Al₂ O₃ -La₂ O₃,TiO₂ -Al₂ O₃ -Co₃ O₄, ZrO₂ -SiO₂ -Al₂ O₃, ZrO₂ -SiO₂ -SnO, ZrO₂ -SiO₂-Nb₂ O₅, ZrO₂ -SiO₂ -WO₃, ZrO₂ -SiO₂ -TiO₂, ZrO₂ -SiO₂ -MoO₃, ZrO₂ -SiO₂-HfO₂, ZrO₂ -SiO₂ -Ta₂ O₅, ZrO₂ -Al₂ O₃ -SiO₂, ZrO₂ -Al₂ O₃ -PbO, ZrO₂-Al₂ O₃ -Nb₂ O₅, ZrO₂ -Al₂ O₃ -WO₃, ZrO₂ -Al₂ O₃ -TiO₂, ZrO₂ -Al₂ O₃-MoO₃, ZrO₂ -HfO₂ -Al₂ O₃, ZrO₂ -HfO₂ -TiO₂, and the like. Othersuitable mixed metal oxides embraced within the scope of this inventionare disclosed by Tanabe et al., Bulletin of the Chemical Society ofJapan, Vol. 47(5), pp. 1064-1066 (1974).

The metal oxides described herein which can be used as performancemoderators in association with the condensation catalyst may contributeto product selectivity and/or catalytic activity of the reaction and/orstability of the catalyst. The catalyst structure can comprise fromabout 0 to about 90 percent or greater by weight of the metal oxide,preferably from about 0 to about 75 percent by weight of the metaloxide, and more preferably from about 0 to about 50 percent by weight ofthe metal oxide, the remainder being the weight of the condensationcatalyst. For mixed metal oxides containing titania, higherconcentrations of titania can provide very desirable PEHA and HETETAselectivities. As discussed hereinafter, the condensation catalyst ofthis invention may also contain support(s), binding agent(s) or otheradditives to stabilize or otherwise help in the manufacture of thecatalyst.

The metallic phosphate and polyphosphate performance moderators may ormay not have a cyclic structure and may or may not have a condensedstructure. Suitable metallic phosphates having a cyclic structure or anacyclic structure are disclosed in U.S. patent application Ser. No.07/390,706, filed Aug. 8, 1989 and incorporated herein by reference.Suitable metallic polyphosphates having a condensed structure aredisclosed in U.S. patent application Ser. No. 07/390,709, filed Aug. 8,1989 and incorporated herein by reference (now U.S. Pat. No. 4,983,736).Illustrative of metallic phosphate and polyphosphate performancemoderators include, for example, metallic orthophosphates (PO₄⁻³)metallic pyrophosphates (P₂ O₇ ⁻⁴), metallic polyphosphates(including tripolyphosphates (P₃ O₁₀ ⁻⁵), tetrapolyphosphates (P₄ O₁₃⁻⁶), pentapolyphosphates (P₅ O₁₆ ⁻⁷) and higher polyphosphates),metallic metaphosphates (including trimetaphosphates (P₃ O₉ ⁻³),tetrametaphosphates (P₄ O₁₂ ⁻⁴) and other lower and highermetaphosphates) and metallic ultraphosphates (condensed phosphatescontaining more P₂ O₅ than corresponds to the metaphosphate structure).Corresponding metallic metaphosphimates, metallic phosphoramidates andmetallic amido- and imidophosphates of the above may also be used asperformance moderators in accordance with this invention. Suitablemetals which can be incorporated into the metallic phosphate andpolyphosphate performance moderators include, for example, Group IAmetals, Group IIA metals, Group IIIB metals, Group IVB metals, Group VBmetals, Group VIB metals, Group VIIB metals, Group VIII metals, Group IBmetals, Group IIB metals, Group IIIA metals, Group IVA metals, Group VAmetals, Group VIA metals and mixtures thereof.

Illustrative of metallic orthophosphates which may be utilized in thisinvention include, for example, NaH₂ PO₄, KH₂ PO₄, RbH₂ PO₄, LiH₂ PO₄,CsH₂ PO₄, MgHPO₄, CaHPO₄, YPO₄, CePO₄, LaPO₄, ThPO₄, MnPO₄, FePO₄, BPO₄,AlPO₄, BiPO₄, Mg(H₂ PO₄)₂, Ba(H₂ PO₄)₂, Mg(NH₄)₂ PO₄, Ca(H₂ PO₄)₂, La(H₂PO₄)₃ and the like. Illustrative of metallic pyrophosphates which may beutilized in this invention include, for example, Na₂ H₂ P₂ O₇, K₂ H₂ P₂O₇, Ca₂ P₂ O₇, Mg₂ P₂ O₇, KMnP₂ O₇, AgMnP₂ O₇, BaMnP₂ O₇, NaMnP₂ O₇,KCrP₂ O₇, NaCrP₂ O₇, Na₄ P₂ O₇, K₄ P₂ O₇, Na₃ HP₂ O₇, NaH₃ P₂ O₇, SiP₂O₇, ZrP₂ O₇, Na₆ Fe₂ (P₂ O₇)₃, Na₈ Fe₄ (P₂ O₇)₅, Na₆ Cu(P₂ O₇)₂, Na₃₂Cu₁₄ (P₂ O₇)₁₅, Na₄ Cu₁₈ (P₂ O₇)₅, Na(NH₄)₂ P₂ O₇, Ca(NH₄)₂ P₂ O₇, MgH₂P₂ O₇, Mg(NH₄)₂ P₂ O₇) and the like. Illustrative of metallicpolyphosphates which may be utilized in this invention include, forexample, NaSr₂ P₃ O₁₀, NaCa₂ P₃ O₁₀, NaNi₂ P₃ O₁₀, Na₅ P₃ O₁₀, K₅ P₃O₁₀, Na₃ MgP₃ O₁₀, Na₃ CuP₃ O₁₀, Cu₅ (P₃ O₁₀)₂, Na₃ ZnP₃ O₁₀, Na₃ CdP₃O₁₀, Na₆ Pb(P₃ O₁₀)₂, Na₃ CoP₃ O₁₀, K₃ CoP₃ O₁₀, Na₃ NiP₃ O₁₀, K₂ (NH₄)₃P₃ O₁₀, Ca(NH₄)₂ P₃ O₁₀, La(NH₄)₃ P₃ O₁₀, NaMgH₂ P₃ O₁₀ and the like.Illustrative of metallic metaphosphates which may be utilized in thisinvention include, for example, Na₃ P₃ O₉, K₃ P₃ O₉, Ag₃ P₃ O₉, Na₄ P₄O₁₂, K₄ P₄ O₁₂, Na₂ HP₃ O₉, Na₄ Mg(P₃ O₉)₂, NaSrP₃ O₉, NaCaP₃ O₉, NaBaP₃O₉, KBaP₃ O₉, Ca₃ (P )₂, Ba(P₃ O₉)₂, Na₂ Ni₂ (P₃ O₉)₂, Na₄ Ni(P₃ O₉)₂,Na₄ Co(P₃ O₉)₂, Na₄ Cd(P₃ O₉)₂ and the like. Illustrative of metallicultraphosphates which may be utilized in this invention include, forexample, CaP₄ O₁₁, Ca₂ P₆ O₁₇, Na₈ P₁₀ O₂₉, Na₆ P₈ O₂₃, Na₂ CaP₆ O₁₇,Na₂ P₄ O₁₁, NaBaP₇ O₁₈, Na₂ P₈ O₂₁, K₄ P₆ O₁₇ and the like. Thepreferred metallic phosphate and polyphosphate performance moderatorsfor use in this invention include Group IA metal dihydrogenorthophosphates, Group IA metal metaphosphates and Group IA metaldihydrogen pyrophosphates, more preferably NaH₂ PO₄, Na₃ P₃ O₉, Na₄ P₄O₁₂ and Na₂ H₂ P₂ O₇. Other suitable metallic phosphate andpolyphosphate performance moderators which are embraced within the scopeof this invention are disclosed by Van Wazer, J. R., Phosphorus and ItsCompounds, Vol. 1, Interscience Publishers, Inc., New York (1958).

The metallic phosphate and polyphosphate performance moderators can beprepared by conventional methods known in the art. Sodium is believed tobe one of a small group of cations effective for stabilizingsix-membered cyclic metaphosphates at their temperatures of fusion(about 625° C.) without decomposition to linear and/or other condensedphosphates including mixtures. The formation of cyclic and acyclicmetallic phosphate and polyphosphate structures appears to depend on thecation ionic size, the coordination number of the cation and the ionicor covalent nature of the metal-oxygen bond.

While not wishing to be bound to any particular theory, it is believedthat those metallic phosphate and polyphosphate performance moderatorsand promoters encompassed within the scope of this invention having acyclic structure and possessing ionic character and/or ion exchangecapacity contribute to desired activity and product selectivity whenused in appropriate amounts as described hereinbelow. While the reactionmixture may initially include one or more metallic phosphates and/ormetallic polyphosphates other than metallic phosphates andpolyphosphates having a cyclic structure and possessing ionic characterand/or ion exchange capacity, it is believed to be desirable that suchmetallic phosphates and polyphosphates having a cyclic structure andpossessing ionic character and/or ion exchange capacity be formed insitu in order to contribute to desired activity and product selectivity.In such instances, the preparation conditions or reaction conditionsshould allow for the formation of metallic phosphates and polyphosphateshaving a cyclic structure and possessing ionic character and/or ionexchange capacity. Mixtures of metallic phosphates and polyphosphateshaving a cyclic structure and possessing ionic character and/or ionexchange capacity with metallic phosphates and polyphosphates havingother than a cyclic structure and other than ionic character and/or ionexchange capacity are believed to contribute to desired activity andproduct selectivity.

Illustrative of Group VIB metal-containing substances which can beutilized as performance moderators in association with the condensationcatalyst are described hereinabove. Such Group VIB metal-containingsubstances can contribute to product selectivity, catalytic activityand/or catalyst stability (mechanical or dimensional strength of thecatalyst). Certain of these Group VIB metal-containing substances mayalso be effective as condensation catalysts for use in this invention.

Illustrative of conventional materials which can be utilized asperformance moderators in association with the condensation catalystinclude a mineral acid or a compound derived from a mineral acid.Suitable for use as performance moderators are one or more phosphoricacid or a salt of phosphoric acid, hydrogen fluoride, hydrofluoric acidor a fluoride salt, sulfuric acid or a salt of sulfuric acid, and thelike. The performance moderator may also be organic esters of phosphoricacid or a salt of phosphoric acid, hydrogen fluoride organic complexes,hydrofluoric acid organic complexes or a fluoride salt organiccomplexes, organic esters of sulfuric acid or a salt of sulfuric acid,and the like. Suitable salts of phosphoric acid include sodiumdihydrogen phosphate, disodium hydrogen phosphate and the like.

A variety of conventional Phosphorus-containing substances may besuitable for use as performance moderators in this invention. Theconventional substances should be capable of functioning as aperformance moderator. Illustrative of conventionalphosphorus-containing substances may include, for example, thosedisclosed in U.S. Pat. No. 4,036,881, U.S. Pat. No. 4,806,517, U.S. Pat.No. 4,617,418, U.S. Pat. No. 4,720,588, U.S. Pat. No. 4,394,524, U.S.Pat. No. 4,540,822, U.S. Pat. No. 4,588,842, U.S. Pat. No. 4,605,770,U.S. Pat. No. 4,683,335, U.S. Pat. No. 4,316,841, U.S. Pat. No.4,463,193, U.S. Pat. No. 4,503,253, U.S. Pat. No. 4,560,798 and U.S.Pat. No. 4,578,517.

Suitable conventional phosphorus-containing substances which can beemployed as performance moderators in this invention include acidicmetal phosphates, phosphoric acid compounds and their anhydrides,phosphorous acid compounds and their anhydrides, alkyl or aryl phosphateesters, alkyl or aryl phosphite esters, alkyl or aryl substitutedphosphorous acids and phosphoric acids, alkali metal monosalts ofphosphoric acid, the thioanalogs of the foregoing, and mixtures of anyof the above.

For purposes of this invention, the phosphorus-containing substancesused as promoters and performance moderators herein should only beemployed in amounts sufficient so as to not adversely affect HETETAproduct selectivity. While not wishing to be bound to any particulartheory, it is believed that phosphorus-containing substances arecatalytically selective for the reaction of HETETA and an alkyleneaminesuch as EDA to higher polyalkylene polyamines. Therefore, the amount ofa phosphorus-containing substance used as a promoter or performancemoderator herein is considered important to achieving amines productshaving a high yield weight percent of PEHA and HETETA.

The amount of the performance moderator of the mineral acid type usedwith the condensation catalyst of the invention is not narrowlycritical. Generally, the amount does not exceed 25 weight percent of theweight of the catalyst. As a rule, it is desirable to use at least 0.01weight percent of the weight of the catalyst. Preferably, the amount ofperformance moderator will range from about 0.2 to about 10 weightpercent of the weight of the catalyst. Most preferably, the amount ofperformance moderator will range from about 0.5 to about 5 weightpercent of the weight of the catalyst.

The amount of performance moderator other than the mineral acid typeused with the condensation catalyst is not narrowly critical. Generally,the amount does not exceed 90 weight percent of the weight of thecatalyst. The amount of performance moderator can range from about 0 toabout 90 or greater weight percent of the weight of the catalyst,preferably from about 0 to about 75 weight percent of the weight of thecatalyst, and more preferably from about 0 to about 50 weight percent ofthe weight of the catalyst. Most preferably, the amount of performancemoderator will range from about 0.5 to about 25 weight percent of theweight of the catalyst.

The performance moderator can be provided to the condensation catalystby conventional procedures known in the art. For example, theperformance moderator can be provided to the catalyst by impregnatingparticles or monolithic structures comprising the catalyst with liquidcomprising the performance moderator. This is a well known procedure inthe art for incorporating additives to a solid support material. Thecondensation catalyst of the invention may be utilized as solid powdersor as fused, bonded or compressed solid pellets, or larger structures inassociation with the one or more metal oxides, or as coated, fused,bonded or compressed solid pellets, or larger structures, compositedwith one or more support materials, in association with one or moremetal oxides. These solid structures may be treated with the performancemoderator by mixing a liquid body of the performance moderator with thesolid structure. For example, the condensation catalyst solids may beslurried in the performance moderator, drained, washed and suctioned toremove excess performance moderator and then dried with heat to removeany volatiles accompanying the performance moderator. The dryingtemperature chosen will depend on the nature of the volatiles to beremoved. Usually, the time/temperature for effecting drying will bebelow the conditions for effecting dehydration to remove bound waterfrom the metal oxide in association with the condensation catalyst.Normally the drying temperature will be greater than about 120° C. andbelow about 600° C. depending on the thermal stability of the catalystor the fusion temperature of the particular phosphate specie used ifany. The drying time will generally go down as the drying temperaturerises and vice versus, and may extend from 5 seconds to about 24 hours.

Alternatively, the performance moderator can be provided to thecondensation catalyst at the time of preparing the catalyst inassociation with one or more metal oxides. For example, one or moremetal oxides may be condensed from their respective hydrolyzablemonomers to the desired oxides to form oxide powders which canthereafter be blended and compressed with the catalyst to form pelletsand larger structures of the metal oxide-containing condensationcatalyst of this invention. The one or more metal oxides which can beused in association with the condensation catalyst in accordance withthis invention can be provided from metal salts which can be heated toform the metal oxide. It is appreciated that the performance moderatorcan be incorporated into the molecular bonding configuration of themetal oxide-containing condensation catalyst by conventional proceduresknown in the art.

The condensation catalysts in association with one or more metal oxidesprior to the optional treatment of the performance moderator may beprepared in a wide variety of ways. For example, one or more metaloxides may be provided as a partial condensate on a support, such as asilica or alpha, beta or gamma alumina, silicon carbide, and the like,and then condensed by heating to effect polymerization to the desiredoxide form. The metal oxide(s) may be condensed from hydrolyzablemonomers to the desired oxide, indeed, to form an oxide powder which canthereafter be compressed in the presence of a condensation catalyst toform pellets and larger structures of the metal oxide-containingcondensation catalyst of the invention. A blend of the powder andcondensation catalyst can be made into a shapeable paste which can beextruded and cut into pellets according to conventional procedures. Theextrudate may thereafter be fired to cure the condensation catalyst andfix the structure. The cut extrudate may be blended with a supportmaterial such as those characterized above, and the blend fired to fusethe metal oxide-containing catalyst to the support.

In a preferred embodiment of this invention, a high surface area silica,germania, titania or zirconia can be slurried with an aqueous solutionof ammonium metatungstate or silicotungstic acid, extruded, and calcinedat a temperature of about 400° C.

A preferred catalyst structure comprises a Group VIB and/or IVB metaloxide having a surface area of at least about 140 m² /gm which may ormay not be bonded to a support material. The term "support," as usedherein and in the claims, means a solid structure which does notadversely affect the catalytic properties of the catalyst and is atleast as stable as the catalyst to the reaction medium. The support canfunction as an amine condensation catalyst independent of thecondensation catalyst used herein, although it may have lower catalyticactivity to the reaction. The support may act in concert with thecatalyst to moderate the reaction. Some supports may contribute to theselectivity of the reaction. The catalyst structure can comprise fromabout 2 to about 60 percent by weight or greater of the support, morepreferably from about 10 to about 50 percent by weight of the support,the remainder being the weight of the metal oxide(s) and condensationcatalyst. Included in the weight of the support is the weight of anybinding agent such as phosphates, sulfates, silicates, fluorides, andthe like, and any other additive provided to stabilize or otherwise helpin the manufacture of the catalyst. The support may be particles aslarge or larger than the catalyst component and "glued" to thecondensation catalyst and/or metal oxide by virtue of a binding medium.

The support may constitute a separate phase in the process of extrudingthe catalytic structure. In this embodiment, the support formingmaterial, preferably as a paste is blended with a paste of thecondensation catalyst and one or more metal oxides or a partialcondensate thereof. The paste may comprise the oxide forms of thesupport and the condensation catalyst, each blended with water, and/orbinding agents. The extrudate of the blend is passed through amultiorificed die and chopped into pellets of the desired sizes. Theparticles may be doughnut shaped, spherical, and the like. Then theparticles are calcined to dry them and complete any condensationreaction in the support and/or the metal oxide-containing condensationcatalyst.

The use of supports for the condensation catalyst provides a number ofsignificant advantages. It has been determined that some of thecondensation catalysts are not as stable in the amines reaction mediawhen utilized over an extended period of time. When the reaction iseffected as a batch reaction, this matter is not a problem. However,when the reaction is effected with the condensation catalyst as part ofa fixed bed in a tubular reactor, the preferred procedure for carryingout the invention, it is desirable to have the catalyst be more stable.When the condensation catalyst is combined with the support, it hasgreater stability for the reaction medium, and therefore, it is betterable to be used in a fixed bed of a continuous reactor. The supportedcatalysts suffer only minimally from the leaching problems that thecatalyst per se may have or the problems that are associated withcertain conventional catalysts, such as acidic phosphorus compounds onsilica.

The reactants used in the condensation process of the invention may beammonia or organic compound containing -NH- and any compound possessingan alcoholic hydroxyl group, subject to the following: theintramolecular condensation of an amino compound produces an aminehaving a lower molecular weight, and the intermolecular condensation ofan amino compound with one or more of another amino compound or acompound containing an alcoholic hydroxyl group produces an amine havinga lower, same or higher molecular weight than the reactants.

Illustrative of suitable reactants in effecting the overall process ofthe invention, include by way of example:

Ammonia

MEA--monoethanolamine

DiHEED--dihydroxyethylethylenediamine

DEA--diethanolamine

EDA--ethylenediamine

MeEDA--methylethylenediamine

EtEDA--ethylethylenediamine

AEEA--N-(2-aminoethyl)ethanolamine

HEP--N-(2-hydroxyethyl)piperazine

DETA--diethylenetriamine

HEDETA--hydroxyethyldiethylenetriamine

HETETA--hydroxyethyltriethylenetetramine

HETEPA--hydroxyethyltetraethylenepentamine

AEP--N-(2-aminoethyl)piperazine

PEHA--pentaethylenehexamine

PEHA Isomers

HEHA--hexaethyleneheptamine

HEHA Isomers

HEOA--heptaethyleneoctamine

HEOA Isomers

HPA--higher polyalkylene polyamines

HPA Isomers

TETA Isomers (TETA's)

TAEA--trisaminoethylamine

TETA--triethylenetetramine

DPE--dipiperazinoethane

DAEP--diaminoethylpiperazine

PEEDA--piperazinoethylethylenediamine

TEPA Isomers (TEPA's)

AETAEA--aminoethyltrisaminoethylamine

TEPA--tetraethylenepentamine

AEDPE--aminoethyldipiperazinoethane

AEDAEP--aminoethyldiaminoethylpiperazine

AEPEEDA--aminoethylpiperazinoethylethylenediamine

iAEPEEDA--isoaminoethylpiperazinoethylethylenediamine

BPEA--bispiperazinoethylamine

The foregoing also can represent the products of the reaction. Forexample, ammonia and MEA are frequently employed to produce EDA alongwith a variety of other amines, most of which are set forth above.Further, alkylene oxides such as ethylene oxide can be employed withammonia and a variety of other amines to produce polyalkylene polyaminesin accordance with this invention.

Glycol compounds can also be employed in the preparation of amines.Glycol compounds embrace diols and polyols. Illustrative of glycolcompounds include alkylene glycols such as ethylene glycol.

The feed space velocity, feed mole ratio and reaction temperature andpressure are not narrowly critical and can vary over a wide range. Theselection of these operating variables is dependent on desiredconversions and product selectivity.

In particular, when DiHEED and EDA are employed as reactants in theprocess of this invention, an increase in DiHEED space velocity orEDA/DiHEED feed mole ratio will decrease conversion, while an increasein temperature will increase conversion. Typically, it is desired tooperate at a high enough pressure to maintain the reactants primarily inthe liquid phase. At a particular DiHEED space velocity, EDA/DiHEED feedmole ratio and temperature, the conversion will generally decrease ifthe pressure is lowered until the flow changes from liquid to vapor.

Lower reaction temperatures generally provide higher selectivity todesired products. As the EDA/DiHEED feed mole ratio increases, theselectivity to desired products increases. The EDA/DiHEED feed moleratio may be used to adjust the relative amounts of PEHA and HETETA. Asthe EDA/DiHEED feed mole ratio is increased, the PEHA to HETETA weightratio increases.

The process may be effected in the liquid or vapor or supercriticalliquid states or mixtures thereof though the actual reaction is believedto occur on the catalyst's solid surface in the absorbed state. In thiscontext, the vapor phase reaction is intended to refer to the generalvapor state of the reactants. Though the reaction conditions may rangefrom subatmospheric to superatmospheric conditions, it is desirable torun the reaction from about 50 psig to about 3,000 psig, preferably fromabout 200 psig to about 2,000 psig.

The temperature of the reaction may be as low as about 125° C. to about400° C. Preferably, the reaction temperature ranges from about 150° C.to about 350° C., and most preferably from about 225° C. to about 325°C.

The reaction may be effected by the incremental addition of one of thereactants to the other or by the joint addition of the reactants to thecatalyst. The preferred process effects the reaction in a continuousmanner over a fixed bed of the condensation catalyst in a tubularreactor. However, the reaction may be carried out by slurrying thecatalyst in the reactants or in a batch mode in an autoclave. An inertsuch as nitrogen, methane, hydrogen and the like can be used in thereaction process.

The process of the invention provides the ability to selectivelygenerate the manufacture of desirable PEHA and HETETA without generatinglarge amounts of cyclic alkyleneamine products. The alkyleneaminesproducers composition of this invention has a PEHA+HETETA to PEEDAweight ratio of greater than about 2.0 and a HETETA to PEHA weight ratioof less than about 10.0.

We claim:
 1. A process for making pentaethylenehexamine andhydroxyethyltriethylenetetramine comprising condensing ethylenediamineand dihydroxyethylethylenediamine in the absence of hydrogen as areactant, under condensation conditions including the presence of acatalytically effective amount of a condensation catalyst consistingessentially of a metatungstate and one or more Group IVB metal oxides,wherein the ethylenediamine to dihydroxyethylethylenediamine feed moleratio is sufficient to provide under condensation conditions an aminesproduct, based on 100 percent of the weight of the amines product andexclusive of any water and/or ammonia and/or feed present,(a) greaterthan about 8.0 weight percent of PEHA, (b) greater than about 10.0weight percent of HETETA, (c) less than about 30.0 weight percent ofPEEHA and HEP, (d) less than about 35.0 weight percent of others, (e) aHETETA to PEHA weight ratio of less than about 10.0, and (f) aPEHA+HETETA to PEEDA weight ratio of greater than about 2.0.
 2. Theprocess of claim 1 wherein the Group IVB metal oxide comprises a highsurface area titanium oxide or zirconium oxide.
 3. The process of claim1 wherein the condensation catalyst has a surface area greater thanabout 70 m² /gm.
 4. The process of claim 2 wherein the titanium oxidecomprises titanium dioxide and the zirconium oxide comprises zirconiumdioxide.
 5. The process of claim 2 wherein the condensation catalyst hasa surface area greater than about 140 m² /gm.
 6. The process of claim 2wherein the condensation catalyst has a surface area greater than about70 m² /gm.
 7. The process of claim 1 wherein the Group IVB metal oxidecomprises from about 25 weight percent to about 90 weight percent of theweight of the catalyst.
 8. The process of claim 1 wherein the Group IVBmetal oxide comprises from about 50 weight percent to about 90 weightpercent of the weight of the catalyst.
 9. The process of claim 1 whereinthe Group IVB metal oxide comprises from about 75 weight percent toabout 90 weight percent of the weight of the catalyst.
 10. The processof claim 1 wherein the condensation catalyst is associated with asupport material.
 11. The process of claim 10 wherein the supportcomprises an alumina material or an alumina-silica material.
 12. Theprocess of claim 10 wherein the support comprises a silica material or asilica-alumina material.
 13. The process of claim 10 wherein the supportcomprises from about 2 to about 50 percent by weight of the condensationcatalyst.
 14. The process of claim 51 wherein the ethylenediamine anddihydroxyethylethylenediamine are condensed in the presence of ammonia.15. The process of claim 1 which is conducted at a temperature of fromabout 125° C. to about 400° C.
 16. The process of claim 1 which isconducted at a pressure of from about 50 psig to about 3000 psig. 17.The process of claim 1 which is effected in the liquid or vapor orsupercritical liquid states.